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    Remarkable Mechanochromism in Blends of a π-Conjugated Polymer P3TEOT: The Role of Conformational Transitions and Aggregation
    (Weinheim : Wiley-VCH, 2020) Zessin, Johanna; Schnepf, Max; Oertel, Ulrich; Beryozkina, Tetyana; König, Tobias A.F.; Fery, Andreas; Mertig, Michael; Kiriy, Anton
    A novel mechanism for well-pronounced mechanochromism in blends of a π-conjugated polymer based on reversible conformational transitions of a chromophore rather than caused by its aggregation state, is exemplified. Particularly, a strong stretching-induced bathochromic shift of the light absorption, or hypsochromic shift of the emission, is found in blends of the water-soluble poly(3-tri(ethylene glycol)) (P3TEOT) embedded into the matrix of thermoplastic polyvinyl alcohol. This counterintuitive phenomenon is explained in terms of the concentration dependency of the P3TEOT's aggregation state, which in turn results in different molecular conformations and optical properties. A molecular flexibility, provided by low glass transition temperature of P3TEOT, and the fact that P3TEOT adopts an intermediate, moderately planar conformation in the solid state, are responsible for the unusual complex mechanochromic behavior. © 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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    Lasing by Template-Assisted Self-Assembled Quantum Dots
    (Weinheim : Wiley-VCH, 2023) Aftenieva, Olha; Sudzius, Markas; Prudnikau, Anatol; Adnan, Mohammad; Sarkar, Swagato; Lesnyak, Vladimir; Leo, Karl; Fery, Andreas; König, Tobias A.F.
    Miniaturized laser sources with low threshold power are required for integrated photonic devices. Photostable core/shell nanocrystals are well suited as gain material and their laser properties can be exploited by direct patterning as distributed feedback (DFB) lasers. Here, the 2nd-order DFB resonators tuned to the photoluminescence wavelength of the QDs are used. Soft lithography based on template-assisted colloidal self-assembly enables pattern resolution in the subwavelength range. Combined with the directional Langmuir–Blodgett arrangement, control of the waveguide layer thickness is further achieved. It is shown that a lasing threshold of 5.5 mJ cm−2 is reached by a direct printing method, which can be further reduced by a factor of ten (0.6 mJ cm−2) at an optimal waveguide thickness. Moreover, it is discussed how one can adjust the DFB geometries to any working wavelength. This colloidal approach offers prospects for applications in bioimaging, biomedical sensing, anti-counterfeiting, or displays.
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    Colloidal Self-Assembly Concepts for Plasmonic Metasurfaces
    (Weinheim : Wiley-VCH, 2019) Mayer, Martin; Schnepf, Max J.; König, Tobias A.F.; Fery, Andreas
    Metallic nanostructures exhibit strong interactions with electromagnetic radiation, known as the localized surface plasmon resonance. In recent years, there is significant interest and growth in the area of coupled metallic nanostructures. In such assemblies, short- and long-range coupling effects can be tailored and emergent properties, e.g., metamaterial effects, can be realized. The term “plasmonic metasurfaces” is used for this novel class of assemblies deposited on planar surfaces. Herein, the focus is on plasmonic metasurfaces formed from colloidal particles. These are formed by self-assembly and can meet the demands of low-cost manufacturing of large-area, flexible, and ultrathin devices. The advances in high optical quality of the colloidal building blocks and methods for controlling their self-assembly on surfaces will lead to novel functional devices for dynamic light modulators, pulse sharpening, subwavelength imaging, sensing, and quantum devices. This progress report focuses on predicting optical properties of single colloidal building blocks and their assemblies, wet-chemical synthesis, and directed self-assembly of colloidal particles. The report concludes with a discussion of the perspectives toward expanding the colloidal plasmonic metasurfaces concept by integrating them with quantum emitters (gain materials) or mechanically responsive structures. © 2018 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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    Plasmonic Properties of Colloidal Assemblies
    (Weinheim : Wiley-VCH, 2021) Rossner, Christian; König, Tobias A.F.; Fery, Andreas
    The assembly of metal nanoparticles into supracolloidal structures unlocks optical features, which can go beyond synergistic combinations of the properties of their primary building units. This is due to inter-particle plasmonic coupling effects, which give rise to emergent properties. The motivation for this progress report is twofold: First, it is described how simulation approaches can be used to predict and understand the optical properties of supracolloidal metal clusters. These simulations may form the basis for the rational design of plasmonic assembly architectures, based on the desired functional cluster properties, and they may also spark novel material designs. Second, selected scalable state-of-the-art preparative strategies based on synthetic polymers to guide the supracolloidal assembly are discussed. These routes also allow for equipping the assembly structures with adaptive properties, which in turn enables (inter-)active control over the cluster optical properties. © 2021 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH
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    Exploiting Combinatorics to Investigate Plasmonic Properties in Heterogeneous Ag-Au Nanosphere Chain Assemblies
    (Weinheim : Wiley-VCH, 2021) Schletz, Daniel; Schultz, Johannes; Potapov, Pavel L.; Steiner, Anja Maria; Krehl, Jonas; König, Tobias A.F.; Mayer, Martin; Lubk, Axel; Fery, Andreas
    Chains of coupled metallic nanoparticles are of special interest for plasmonic applications because they can sustain highly dispersive plasmon bands, allowing strong ballistic plasmon wave transport. Whereas early studies focused on homogeneous particle chains exhibiting only one dominant band, heterogeneous assemblies consisting of different nanoparticle species came into the spotlight recently. Their increased configuration space principally allows engineering multiple bands, bandgaps, or topological states. Simultaneously, the challenge of the precise arrangement of nanoparticles, including their distances and geometric patterns, as well as the precise characterization of the plasmonics in these systems, persists. Here, the surface plasmon resonances in heterogeneous Ag-Au nanoparticle chains are reported. Wrinkled templates are used for directed self-assembly of monodisperse gold and silver nanospheres as chains, which allows assembling statistical combinations of more than 109 particles. To reveal the spatial and spectral distribution of the plasmonic response, state-of-the-art scanning transmission electron microscopy coupled with electron energy loss spectroscopy accompanied by boundary element simulations is used. A variety of modes in the heterogeneous chains are found, ranging from localized surface plasmon modes occurring in single gold or silver spheres, respectively, to modes that result from the hybridization of the single particles. This approach opens a novel avenue toward combinatorial studies of plasmonic properties in heterosystems. © 2021 The Authors. Advanced Optical Materials published by Wiley-VCH GmbH
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    Comparison of nanotubes produced by fixed bed and aerosol-CVD methods and their electrical percolation behaviour in melt mixed polyamide 6.6 composites
    (Barking : Elsevier, 2010) Krause, Beate; Ritschel, M.; Täschner, C.; Oswald, S.; Gruner, W.; Leonhardt, A.; Pötschke, Petra
    The electrical percolation behaviour of five different kinds of carbon nanotubes (CNTs) synthesised by two CVD techniques was investigated on melt mixed composites based on an insulating polyamide 6.6 matrix. The electrical percolation behaviour was found to be strongly dependent on the properties of CNTs which varied with the synthesis conditions. The lowest electrical percolation threshold (0.04 wt.%) was determined for as grown multi-walled carbon nanotubes without any purification or chemical treatment. Such carbon nanotubes were synthesised by the aerosol method using acetonitrile as ferrocene containing solvent and show relatively low oxygen content near the surface, high aspect ratio, and good dispersability. Similar properties could be found for nanotubes produced by the aerosol method using cyclohexane, whereas CNTs produced by the fixed bed method using different iron contents in the catalyst material showed much higher electrical percolation thresholds between 0.35 and 1.02 wt.%. © 2009 Elsevier Ltd. All rights reserved.
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    Electrical and thermal properties of polyamide 12 composites with hybrid fillers systems of multiwalled carbon nanotubes and carbon black
    (Barking : Elsevier, 2011) Socher, Robert; Krause, Beate; Hermasch, Sylvia; Wursche, Roland; Pötschke, Petra
    Hybrid filler systems of multiwalled carbon nanotubes (MWCNTs) and carbon black (CB) were incorporated into two types of polyamide 12 (PA12) using small-scale melt mixing in order to identify potential synergistic effects on the interaction of these two electrical conductive fillers. Although no synergistic effects were observed regarding the electrical percolation threshold, at loadings well above the percolation threshold higher volume conductivities were obtained for samples containing both, MWCNT and CB, as compared to single fillers. This effect was more pronounced when using a higher viscous PA12 matrix. The formation of a co-supporting network can be assumed. The combined use of CB and MWCNTs improved the macrodispersion of MWCNT agglomerates, which can be assigned as a synergistic effect. DSC measurements indicated an effect of the nanofiller on crystallisation temperatures of PA12; however this was independent of the kind or amount of the carbon nanofiller. © 2011 Elsevier Ltd.
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    Ultralow percolation threshold in polyamide 6.6/MWCNT composites
    (Barking : Elsevier, 2015) Krause, Beate; Boldt, Regine; Häußler, Liane; Pötschke, Petra
    When incorporating multiwalled carbon nanotubes (MWCNTs) synthesised by the aerosol-CVD method using different solvents into polyamide 6.6 (PA66) by melt mixing an ultralow electrical percolation threshold of 0.04. wt.% was found. This very low threshold was assigned to the specific characteristic of the MWCNTs for which a very high aspect ratio, a good dispersability in aqueous surfactant dispersions, and relatively low oxygen content near the surface were measured. The investigation of the composites by transmission electron microscopy on ultrathin cuts as well as by scanning electron microscopy combined with charge contrast imaging on compression moulded plates illustrated a good MWCNT dispersion within the PA66 matrix and that the very high aspect ratio of the nanotubes remained even after melt processing. Additionally, the thermal behaviour of the PA66 composites was investigated using differential scanning calorimetry (DSC) showing that the addition of only 0.05. wt.% MWCNT leads to an increase of the onset crystallization temperature of 11. K.
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    Influence of dry grinding in a ball mill on the length of multiwalled carbon nanotubes and their dispersion and percolation behaviour in melt mixed polycarbonate composites
    (Barking : Elsevier, 2011) Krause, Beate; Villmow, Tobias; Boldt, Regine; Mende, Mandy; Petzold, Gudrun; Pötschke, Petra
    Ball milling of carbon nanotubes (CNTs) in the dry state is a common way to produce tailored CNT materials for composite applications, especially to adjust nanotube lengths. For NanocylTM NC7000 nanotube material before and after milling for 5 and 10h the length distributions were quantified using TEM analysis, showing decreases of the mean length to 54% and 35%, respectively. With increasing ball milling time in addition a decrease of agglomerate size and an increase of packing density took place resulting in a worse dispersability in aqueous surfactant solutions. In melt mixed CNT/polycarbonate composites produced using masterbatch dilution step, the electrical properties, the nanotube length distribution after processing, and the nano- and macrodispersion of the nanotubes were studied. The slight increase in the electrical percolation threshold in the melt mixed composites with ball milling time of CNTs can be assigned to lower nanotube lengths as well as the worse dispersability of the ball milled nanotubes. After melt compounding, the mean CNT lengths were shortened to 31%, 50%, and 66% of the initial lengths of NC7000, NC7000-5h, and NC7000-10h, respectively. © 2011 Elsevier Ltd.
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    Cellulose-carbon nanotube composite aerogels as novel thermoelectric materials
    (Amsterdam [u.a.] : Elsevier, 2018) Gnanaseelan, Minoj; Chen, Yian; Luo, Jinji; Krause, Beate; Pionteck, Jürgen; Pötschke, Petra; Qu, Haisong
    Thermoelectric materials based on cellulose/carbon nanotube (CNT) nanocomposites have been developed by a facile approach and the effects of amount (2–10 wt%) and types of CNTs (single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs)) on the morphology (films and aerogels) and the thermoelectric properties of the nanocomposites have been investigated. Composite films based on SWCNTs showed significantly higher electrical conductivity (5 S/cm at 10 wt%) and Seebeck coefficient (47.2 μV/K at 10 wt%) compared to those based on MWCNTs (0.9 S/cm and 11 μV/K, respectively). Lyophilization, leading to development of aerogels with sub-micron sized pores, decreased the electrical conductivity for both types by one order of magnitude, but did not affect the Seebeck coefficient of MWCNT based nanocomposites. For SWCNT containing aerogels, higher Seebeck coefficients than for films were measured at 3 and 4 wt% but significantly lower values at higher loadings. CNT addition increased the thermal conductivity from 0.06 to 0.12 W/(m∙K) in the films, whereas the lyophilization significantly reduced it towards values between 0.01 and 0.09 W/(m∙K) for the aerogels. The maximum Seebeck coefficient, power factor, and ZT observed in this study are 49 μV/K for aerogels with 3 wt% SWCNTs, 1.1 μW/(m∙K2) for composite films with 10 wt% SWCNTs, and 7.4 × 10−4 for films with 8 wt% SWCNTs, respectively.